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Volumn 99, Issue 2-3, 1999, Pages 391-418

Solvent Density Inhomogeneities in Supercritical Fluids

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EID: 0001576267     PISSN: 00092665     EISSN: None     Source Type: Journal    
DOI: 10.1021/cr9700437     Document Type: Article
Times cited : (388)

References (185)
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    • Antal, M. J., Jr.; Brittain, A.; DeAleida, C.; Ramayya, S.; Roy, J. C. In Supercritical Fluids; Squires, T. G. and Paulaitis, M. E., Eds.; ACS Symposium Series 329, American Chemical Society: Washington, 1987.
    • (1987) Supercritical Fluids
    • Antal M.J., Jr.1    Brittain, A.2    Dealeida, C.3    Ramayya, S.4    Roy, J.C.5
  • 11
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    • note
    • The scaling axis is the analytic continuation of the gas-liquid coexistence curve into the supercritical regime.
  • 12
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    • Proceeding, Stellenbosch, South Africa; Lecture Notes in Physics 186; Hahne, F. J. W., Ed.; Springer-Verlag: Stellenbosh, South Africa
    • Fisher, M. E. In Critical Phenomena; Proceeding, Stellenbosch, South Africa; Lecture Notes in Physics 186; Hahne, F. J. W., Ed.; Springer-Verlag: Stellenbosh, South Africa, 1983.
    • (1983) Critical Phenomena
    • Fisher, M.E.1
  • 13
    • 0346751205 scopus 로고    scopus 로고
    • note
    • Even in the absence of critical fluctuations one may see short length scale (generally first solvation shell) density inhomogeneities (typically enhancements) as a direct consequence of the intermolecular forces; such effects are frequently important at low densities. The relationship between local density enhancements which may arise in the absence of critical fluctuations and those which are a direct consequence of critical fluctuations is not very well understood. Observed density enhancements will most probably reflect both possible origins, with the relative importance of each being dependent upon the state point being considered and the strength of the attractive solute-solvent interactions. Some initial efforts aimed at understanding this relationship can be found in ref 64.
  • 32
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    • Kajimoto, O. Chem. Rev. 1999, 99, 355 (this issue).
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    • Johnston, K. P., Penninger, J. M. L., Eds.; ACS Symposium Series 406; American Chemical Society: Washington
    • Johnston, K. P.; Kim, S.; Combes, J. In Supercritical Fluid Science and Technology; Johnston, K. P., Penninger, J. M. L., Eds.; ACS Symposium Series 406; American Chemical Society: Washington, 1989.
    • (1989) Supercritical Fluid Science and Technology
    • Johnston, K.P.1    Kim, S.2    Combes, J.3
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    • McNally, M. E. P.; Bright, F. V. In Supercritical Fluid Technology; McNally, M. E. P., Bright, F. V., Eds.; ACS Symposium Series 488; American Chemical Society: Washington, 1992.
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  • 48
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    • note
    • u → 0.
  • 50
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    • Reference 10 errs in this regard
    • Reference 10 errs in this regard.
  • 52
    • 0346120583 scopus 로고    scopus 로고
    • note
    • Although measurements of partial molar properties contain contributions from both short- and long-range density inhomogeneities, the contribution of the long-range inhomogeneities diverges with the compressibility. As a result, the short-range contribution to partial molar properties becomes inconsequential as the critical point is approached.
  • 70
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    • note
    • The partial molar volume of a solute at infinite dilution can be written as the sum of two contributions. The first is the finite solvent-partial molar volume, i.e. the volume change that would result from addition of a solvent molecule. The second contribution arises because the solvent environment induced by the introduction of a solute molecule differs from the environment found around a solvent molecule. Note that as a result of indirect effects, the environment around solute and solvent molecules may differ out to very long distances from the central molecule. As a result, this second contribution scales as the isothermal compressibility of the solvent, and it diverges at the solvent's critical point.
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    • Personal communication
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    • Squires, T. G., Paulaitis, M. E., Eds.; ACS Symposium Series 329; American Chemical Society: Washington
    • Kim, S.; Johnston, K. P. In Supercritical Fluids; Squires, T. G., Paulaitis, M. E., Eds.; ACS Symposium Series 329; American Chemical Society: Washington, 1987.
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  • 106
    • 0347381546 scopus 로고    scopus 로고
    • note
    • Note that in ref 72 there is significant scatter in the data, while in ref 93 the supposedly same data presented in both Figures 13 and 14 of this reference is not self-consistent.
  • 112
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    • note
    • 47 expression for the free energy of solvation is written relative to the free energy of the ideal solution.
  • 120
    • 0347381543 scopus 로고    scopus 로고
    • Figure 7 of ref 119 and Figure 4a of ref 118 disagree
    • Figure 7 of ref 119 and Figure 4a of ref 118 disagree.
  • 122
    • 0346120581 scopus 로고    scopus 로고
    • In ref 36, the curves in Figure 15 appear to have been mislabeled, see Figure 16
    • In ref 36, the curves in Figure 15 appear to have been mislabeled, see Figure 16.
  • 127
    • 0346751200 scopus 로고    scopus 로고
    • note
    • r) curves, even given the same choice of cutoff values. In particular, the maximum values attained for ρ̃/ are nearly the same in the two studies, but the positions of the maxima occur at much higher densities in ref 47. Possible sources of this discrepancy are (1) the use of integral equations with the Percus-Yevick closure in ref 47, whereas molecular dynamics simulation was used in ref 46 and/or (2) the use of different choices for the excluded volume of the solute when computing ρ̃/.
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    • note
    • The agreement in ref 141 is not as good, presumably because the simulation temperature was not corrected for the critical point of the water model used.
  • 149
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    • Balbuena, P. B.; Johnston, K. P.; Rossky, P. J. J. Phys. Chem. 1995, 99, 1554; J. Am. Chem. Soc. 1994, 116, 2689.
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    • The potentials used differ slightly, see refs 121 and 168
    • The potentials used differ slightly, see refs 121 and 168.
  • 180
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    • Bright, F. V., McNally, M. E. P., Eds.; ACS Symposium Series 488; American Chemical Society: Wasington
    • Betts, T. A.; Zagrobelny, J.; Bright, F. V. In Supercritical Fluid Technology; Bright, F. V., McNally, M. E. P., Eds.; ACS Symposium Series 488; American Chemical Society: Wasington, 1992.
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    • note
    • 80 definition of the identity persistence time differs from that of refs 167 and 113.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.